Vat dyestuffs of the pyranthrone series



Patented July 15, 1952 PATENT OFFICE VAT DYESTUFFS'OF THE PYRANTHRONE I sERIEs V 7 Karl Saf ti en and Anton Vilsmeier, Ludwigshafenon-the-Rhine, Germany w I No Drawing. Application December 2 9 1949, Se rial No. 135,838. In Germany October 1,1948

The present invention relates to new vat dyestuffs of the pyranthrone series which are valuable for dyeing different kinds of textiles and other-materials. 7

We have found that valuable vat dyestuffs of the pyranthrone series are obtained by condensing halogen pyranthrones with l-aminoanthraquinoneZ-aldehyde; -Among the halogen pyranthrones,;the;dito tetra-halogen pyranthrones, which-are readily accessible commercially, are especially. suitable, but still. morev highly halogenated pyranthrones may also be used for the process. The employment. of bromo-pyranthrones is especially advantageous. 3.

. Thereaction is carried outininertsolvents or .diluents in the presence of acid-bindingilagents, such as sodium or potassium carbonate, and of copperor copper compounds, such as copperoxide. In some cases it is advantageous-to use copper oxide alone which has an acid-binding as well as a catalytic action.

There are thus obtained vat dyestuffs having excellent fastness properties and which give redbrown to violet-tinged brown shades depending on the ratio of halogen pyranthrone to l-aminoanthraqu-inone-Z-aldehyde employed.

The exact constitution of the new-products has not been hitherto established. However, we know that the new dyestuffs are not simple imides, but probably belong to the acridine series.

The following examples will further illustrate the invention but the inventionisnot. limited to these-examples". The parts are by weight.

Example 1 -A mixtnre of55 parts (1.1 mols of 1--aminoanthraquinone 2-al'dehydeand 21* parts of copper: oxide isintroduced' while stirring into a mixture, heated to 150 C.,-oi 113 parts (1 mol) of dibromo-pyranthrone (prepared according to U." S;. 'Pate nt"9'55,1-05), 134Q"parts .of' naphthalene and 42 parts of" anhydrous sodium carbonate, and the,whole is. heated to boiling until' l 'aminoanthraiqui'rione z-aldehyde can no longer be detected. The whole is thenallowed to cool to 120 C., diluted with monochlorbenzene and filtered. by suction at 90 C. The residue is freed from adherent solvent and inorganic compounds by known methods. The dried. dyestuff is a dark powder which'di'ssolves in concentrated sulphuric acidto give a blue coloration. The dyestuff dyes cotton well-covering red-brown shades of excellent fastness properties from a red-violet vat.

Dyestuffs having similar properties are obtained by using dichloropyranthrone or chlorobromopyranthrone instead of. dibromopyranthrone; H v

4' Claims. (01. 2605-274) I Example 2 I .;A- mixture of parts (2.6 mole) of. l-amino- .anthraquinone-2-aldehyde and 43- parts of. cop-- peroxidelis introduced while stirring into a mixture, heated to 0., of 113' parts ('1 mol) of dibromopyranthrone, 1340 parts of naphthalene and 64 parts of anhydrous sodium carbonateand the whole is heated to boiling until dibromopyranthrone can no longerbe detected. After working up in the manner described in Example 1 there is obtained a dark powder which dissolves in concentrated sulphuric acid. to give a grey-blue coloration. The dyestuff dyes cotton very fast currant-brown shades from a reddish violet vat. It is especially suitable for printing cotton and for coloring viscose :solutions which are to be worked up into artificial silk.

Example 3 A mixture of 55 parts 61.1 mols) of l-aminoanthraq uinone-2-aldehyde and 21 parts'of cop'- per oxide is introduced while. stirring into a mixture, heated to 150 C., of 128 parts (.1 mol) of tribromopyranthrone (prepared. according to U. S; Patent- 955,105) 13'40Zparts. of naphthalene and 42 parts of anhydrous sodium carbonate, and the whole is heatedto'b'oiling while stirring until l-aminoanth'raquinone-2-aldehyde can no long;- erbe detected; After working up in the'usual manner; adyestuff is obtained; which dyes cotton powerful red-brown shades from a'red-violet Vat. I

13y using-2 mole of" l-aminoanthraquinone-2 aldehyde for eachmol of tribromopyranthrone, a vat dyestuff'is-obtained which dissolves in concentratedsulphuric acid to give an olive-green coloration and dyes cotton from a red-violet vat currant -brownsha'des, and by using 3'mo1s of 1-aminoanthraquinone-2-aldehyde the vat dyestuff obtained. dyes cotton reyish-brownshades. More highlyhalogenated pyranthrones may also be reacted with one or more mole ofl-aminoanthraquinone-Z-aldehyde in the same way. Vat dyestuffs are thus obtained which dye cotton red-brown to grey-brown shades.

Example 4 A mixture of 10 parts of l-aminoanthraquinone1-2-aldehyde and 4.2 parts of copper oxide is introduced while stirring into a mixture, heated to 150 C., of 260 parts of naphthalene, 18

.parts; of chloropyranthrone having a chlorine content of 12.5 per cent (obtained by the reaction of sulphuryl chloride on pyranthrone in nitrobenzene in the presence of iodine) and 8.4 parts of anhydrous; sodium carbonate and the whole is heated. to boiling untilinitiall material can nolonger be detected. Afterworking'up. in the manner. described in. Example 11,, a dark powder isobtained which. dissolves in concentrated.

3 sulphuric acid giving a blue coloration. The dyestuff dyespotton powerful yellow-brown shades of excellent fastn'ess properties from a red-violet vat.

Example 5 A mixture of 21.6 parts (2.2 idols) of l-amino anthraquinone-2-aldehyde and 8.6 parts of copper oxide is introduced into a mixture, heated to;

150 C., of 358 parts of naphthalene, 2 1.8 parts i oration. The dyestufi dyes-cotton currant-b'rown *shadesof excellent fastness properties from a blue-violet vat.

What we claim is: 1.: A vat dyestulf of the pyranthrone series corresponding to the general formula Item I n I O v wherein n is a member'in the series of l to 4 and the pyranthrone nucleus may contain up to three halogen atoms selected from the class consisting of chlorine and bromine atoms, which dyestuffs dye cotton from the vat in shades ranging from red-brown to violet-brown, and are identical with the products obtained by heating a halogenated pyranthrone containing up to four halogen atoms, the halogen atoms being selected from the class consisting of chlorine and brominewith at .most four molecular proportions of l-am inoanthraquinone-z-aldehyde in presence of an inert diluent, an acid-binding agent and a copper compound at temperatures of about 200? C;, said halogenated -;pyranthrones being obtained.- by halogenating pyranthrone until at most four halogenatoms have been introduced.

2; The vatdyestufi of the pyranthrone series corresponding to the general formula said dyestuff being soluble in concentrated sulfuric acid to give ablue' coloration, and dyeing cotton red-brown shades from a red-violet vat and-being identical with'the product'obtained by heating 1 mole of dibromopyranthrone with V saiddyestufi being 1 mole of 1-amino-anthraduinone kaldehyde in presence of an inert diluent, 'an'acid-binding agent and a copper compound at temperatures of about 200 C., said dibromopyranthrone being obtained by brominating pyranthrone until two bromine'atoms have been introduced. Q 3. The vat dyestufi of the pyranthrone series corresponding to the general formula t I said dyestuff being soluble inconcentrated sulfuric acid to give a grey-blue coloration, and dyeing cotton currant-brown shades from a reddish-violet vat and being identical with'the product obtained by heating 1 mole of dibromopyranthrone with 2 moles'of l-amino-anthraquinone 2-aldehyde inpresence of an inert diluent, an acid binding agent and a copper compound at temperatures of about 200 C., said dibromopyranthrone being obtained by brominating pyranthrone until two bromine atoms have been introduced.

4. The'vat dyestuff of the pyranthrone serie corresponding to the general formula O soluble in concentrated sulfuric acid'to give an olive-green coloration, and dyeing cotton currant-brown shades from a redviolet vat, being identical with the product obtained by heating 1 mole of tribromopyranthrone with 2 moles of 1-amino-anthraquinone-2-aldehyde in presence of an inert diluent, an acidbinding agent and a copper compound at temperatures of about 200 0., said tribromopyranw throne being obtained by brominating pyranthrone until three bromine atoms havebeen introduced. r 1 .T R F T E ANTON VILSMEIER,

REFERENCES CITED The following references are of record'in file of this patent:

the

Number Name 1,801,709 Zerweck et a1 Apr. 21 1931 1,861,921 Honold -June,7, 1932 FOREIGN PATENTS V Number Country Qate 145,888 Switzerland June-1, l 93l 472,325 Great Britain Sept. 22, 1937 

1. A VAT DYESTUFF OF THE PYRANTHRONE SERIES CORRESPONDING TO THE GENERAL FORMULA WHEREIN N IS A MEMBER IN THE SERIES OF 1 TO 4 AND THE PYRANTHRONE NUCLEUS MAY CONTAIN UP TO THREE HALOGEN ATOMS SELECTED FROM THE CLASS CONSISTING OF CHLORINE AND BROMINE ATOMS, WHICH DYESTUFFS DYE COTTON FROM THE VAT IN SHADES RANGING FROM RED-BROWN TO VIOLET-BROWN, AND ARE IDENTICAL WITH THE PRODUCTS OBTAINED BY HEATING A HALOGENATED PYRANTHRONE CONTAINING UP TO FOUR HALOGEN ATOMS, THE HALOGEN ATOMS BEING SELECTED FROM THE CLASS CONSISTING OF CHLORINE AND BROMINE WITH AT MOST FOUR MOLECULAR PROPORTION OF 1-AMINOANTHRAQUINONE-2-ALDEHYDE IN PRESENCE OF AN INERT DILUENT, AND ACID-BINDING AGENT AND A COPPER COMPOUND AT TEMPERATURES OF ABOUT 200* C., SAID HALOGENATED PYRANTHRONES BEING OBTAINED BY HALOGENATING PYRANTHRONE UNTIL AT MOST FOUR HALOGEN ATOMS HAVE BEEN INTRODUCED. 